US2908694A - 7-substituted thio-4-androstenes - Google Patents
7-substituted thio-4-androstenes Download PDFInfo
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- US2908694A US2908694A US804106A US80410659A US2908694A US 2908694 A US2908694 A US 2908694A US 804106 A US804106 A US 804106A US 80410659 A US80410659 A US 80410659A US 2908694 A US2908694 A US 2908694A
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- United States
- Prior art keywords
- methylthiotestosterone
- acetoxy
- preparation
- androstenes
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 150000001875 compounds Chemical class 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000003431 steroids Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000001589 carboacyl group Chemical group 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000005108 alkenylthio group Chemical group 0.000 description 2
- 229940124325 anabolic agent Drugs 0.000 description 2
- 239000003263 anabolic agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000027932 Collagen disease Diseases 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003862 glucocorticoid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- -1 methylthio-4- androsten-3-one Chemical compound 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960003604 testosterone Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J31/00—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
Definitions
- This invention relates to new steroids of the androstene-series. More particularly, it relates to7-alkylthio- 4-androstenes and 7-alkenylthio l-androstenes land methods of preparing .the same.
- R is a member of the group consisting of hydrogen, lower ,alkanoyl, cycloalkyl lower alkanoyLand aroyl radicals and R is a member of the group consisting of lower alkyl and lower alkenyl radicals.
- the compoundscf the present invention are crystalline solids having relatively high melting points. They are relatively insolublein water and somewhat soluble in the usual organic solvents. They are crystallizable from mixtures of ketones and hydrocarbon solvents.
- the present compounds are prepared by reacting a 17fl-lower alkanoyl-4,6-androstadiene-3-one with a lower alkyl or lower al-kenyl mercaptan.
- the reaction is preferably carried out in a solvent such as glacial acetic acid in the presence of a mineral acid catalyst.
- the reaction takesplace at a-tempenaturebetweenO and 50 C. and is usually complete in a matter of 2 or 3 hours to several days.
- the product is recovered by evaporation of the solvent used in. the reaction followed by taking up the residue in a further organicsolvent. Following removal of the latter solvent, the desired product is further purified by crystallization.
- the process of this invention proceeds under steric influences and stereoisomers are formed, howev er, one is obtained inpredominate amount.
- the isomer obtained in predominant amount has in each case been characterized herein as possessing the alpha configuration of the 7 lower la-lkylthio or lower alkenylthio group.
- This configuration has been designated in order to provide a more complete exposition of the present invention, and in order that the specification shall constitute a more useful contribution to the art.
- the designated configuration ofthe 7'-lower alkylthio or lower alkenylthio group is based uponsan analysis of molecular rotation data presently appearing in the chemical literature, and is therefore not to be interpreted except in relation to the-state of the, artpresently known to organic chemists. It will be apparent that no part of the specification will be materially defective if it should later 'be in the field.
- the compounds of the present invention can be used in'the form of tablets, fills, powders, and so forth, which .mayhlso contain starch, excipients, and other ingredients necessary in the compounding of such dosage forms. .They may 'be used singly or in combination with other steroids.
- lower alkyl radical is intended to cover saturated hydrocarbon radicals having 1 to 6 carbon atoms.
- lower a-lkanoyl radical is intended to cover the acyl radicals obtained from alkanoic acids. having 1 to 14 carbon atoms and the term cycloalkyl lower alkanoyl radical is intended to cover acyl radicals obtained from cycloalkyl substituted alkanoic acids having 7 to 11 carbon atoms with .5 101'. 6 carbon atoms in the cycloalkyl group.
- EXAMPLE 5 Preparation of 17p-acetogcy-7a-n-propylthi0-4-androsten- -one A solution of 0.6 g. of 17/3-acetoxy-4,6-androstadien-3- one, 1 ml. of concentrated hydrochloric acid and 5 ml. of isopropylmercaptan in 25 ml. of glacial acetic acid is treated according to the procedure described in Example 1 to give 17 3-acetoxy-7u-isopropylthio-4-androsten-3-one.
- EXAMPLE 7 Preparation of 7a-methylthiotestosterone propionate A solution of 1.0 g. of 7a-methylthiotestosterone in ml. of reagent pyridine is treated with 5 ml. of propionic anhydride and allowed to stand overnight at room temperature. The mixture is poured into water, extracted with methylene chloride, the methylene chloride extract washed successively with saturated sodium bicarbonate solution and water, and finally evaporated to dryness under reduced pressure to furnish 7a-methylthiotestosterone propionate as white crystals;
- EXAMPLE 8 Preparation of 7a-methylthiotestosterone isobutyrate A solution of 0.5 g. of 7a-methylthio-testosterone in 5 ml. of reagent pyridine is treated with 3 g. of isobutyric anhydride according to the procedure described in Example 7 to give 7a-methylthiotestosterone isobutyrate;
- a 239 mp max (e14,800); 1 1730, 1670, 1625, 1195 cm.-
- EXAMPLE 11 Preparation of 7a-methylthiotestosterone decanoate A solution containing 1 g. of 7u-methylthiotestosterone in 25 ml. of dry benzene is treated with 3 ml. of dry pyridine and 4 g. of decanoyl chloride according to the procedure described in Example 10 to give 7oc-methylthiotestosterone decanoate;
- R is a member of the group consisting of hydrogen, lower alkanoyl, cycloalkyl lower alkanoyl and aroyl radicals and R is a member of the group consisting of lower alkyl and lower alkenyl radicals.
- R is a lower alkanoyl radical and R is a lower alkyl radical.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
L difi i Patented Oct. 13, 1959 United states Patent Ofice r 7-sIJBs'rITUr D THI'G-d-ANDROSTENES Robert Sc'ha u'b, Parainus, and Martin J. Weiss, Oradell, N.J., assignors to American Cyanamid Company, New York, N.Y., acorporation of Maine No' Drawing. Application April 6, 1959 Serial No. 804,106
"6 Claims.' (Cl. 260-'397.4)
This invention relates to new steroids of the androstene-series. More particularly, it relates to7-alkylthio- 4-androstenes and 7-alkenylthio l-androstenes land methods of preparing .the same.
The .use of steroids for their glucocorticoid activity in the treatment of collagen diseases is well :known. Their use, however, as .nonor low-virilizing anabolic agents is less well known. Wehave now found t-hatthe steroids described hereinafter possess these properties and are therefore useful as anabolic agents.
The compoundsof the present invention may be illustrated by the general formula:
in which R is a member of the group consisting of hydrogen, lower ,alkanoyl, cycloalkyl lower alkanoyLand aroyl radicals and R is a member of the group consisting of lower alkyl and lower alkenyl radicals.
The compoundscf the present invention are crystalline solids having relatively high melting points. They are relatively insolublein water and somewhat soluble in the usual organic solvents. They are crystallizable from mixtures of ketones and hydrocarbon solvents.
The present compounds are prepared by reacting a 17fl-lower alkanoyl-4,6-androstadiene-3-one with a lower alkyl or lower al-kenyl mercaptan. The reaction is preferably carried out in a solvent such as glacial acetic acid in the presence of a mineral acid catalyst. The reaction takesplace at a-tempenaturebetweenO and 50 C. and is usually complete in a matter of 2 or 3 hours to several days. The product is recovered by evaporation of the solvent used in. the reaction followed by taking up the residue in a further organicsolvent. Following removal of the latter solvent, the desired product is further purified by crystallization.
The process of this invention proceeds under steric influences and stereoisomers are formed, howev er, one is obtained inpredominate amount. The isomer obtained in predominant amount has in each case been characterized herein as possessing the alpha configuration of the 7 lower la-lkylthio or lower alkenylthio group. This configuration has been designated in order to provide a more complete exposition of the present invention, and in order that the specification shall constitute a more useful contribution to the art. However, the designated configuration ofthe 7'-lower alkylthio or lower alkenylthio group is based uponsan analysis of molecular rotation data presently appearing in the chemical literature, and is therefore not to be interpreted except in relation to the-state of the, artpresently known to organic chemists. It will be apparent that no part of the specification will be materially defective if it should later 'be in the field.
The compounds of the present invention can be used in'the form of tablets, fills, powders, and so forth, which .mayhlso contain starch, excipients, and other ingredients necessary in the compounding of such dosage forms. .They may 'be used singly or in combination with other steroids.
In the present application the term lower alkyl radical is intended to cover saturated hydrocarbon radicals having 1 to 6 carbon atoms. The term lower a-lkanoyl radical is intended to cover the acyl radicals obtained from alkanoic acids. having 1 to 14 carbon atoms and the term cycloalkyl lower alkanoyl radical is intended to cover acyl radicals obtained from cycloalkyl substituted alkanoic acids having 7 to 11 carbon atoms with .5 101'. 6 carbon atoms in the cycloalkyl group.
' The following examples illustrate in detail the prepara- ,tion.of the 7-allcylthioand 7-alkenylthioandrostenes of ,the. present invention.
EXAMPLE 1 Preparation of 17,8-acet0xy-7a-methylthio-4-androsten-3- one A solution of 0.6 g. of 17/3-acetoxy-4,6-androstadien- 3-one [C. Djerassi et -al., J. Am. Chem. Soc., 72, 4538 (l-950)], 1 ml. of concentrated hydrochloric acid and 5 ml. of methylmercaptan in 25 m1. of glacial acetic acid is allowed to stand at 58 C. for 48 hours. The reaction miXture is evaporated to dryness under reduced pressure and the-concentrate is diluted with methylene chloride and washed with excess. saturated sodium bicarbonate solution, and then with water. The organic phase is dried with anhydrous magnesium sulfate and evaporated to dryness under reduced pressure to give a glass. Crystallization from acetone-petroleum ether gives 17fl-acetoxy 7oz methylthio-4- androsten-3-one. Recrystallization from acetone-petroleum ether afiords white crystals XE SQ 240 inn (e=1 5,500); 1/ 1730, 1675, 1620, 1240 (cm- EXAMPLE 2 Preparation of .7 7 B-acetoxy 7a ethylzhi0-4-andr0sten-3- one A solution of 0.865 g. of 17pacetoxy-4,6-androstien- 3-one, '2 ml. of concentrated hydrochloric acid and 10 ml. ,OfethyImerCaptan in 75 ml. of glacial acetic acid is allowed to stand at 58 C. for 72 hours. The reaction mixtureis evaporated to dryness under reduced pressure and the concentrateis diluted with methylene chloride and washed with excess. saturated sodium bicarbonate solution, and then with Water. The organic phase is dried with anhydrous magnesium sulfate and evaporated rto (dryness under reduced pressure to give a glass. Crystallization from acetone-petroleum ether gives 17,8- acetoxy 7a ethylthio-4-androsten-3 -one. Recrystallization from acetone-petroleum ether gives white crystals;
A E Q4O m 15,800); 11 1730, 1675; 1620, '1240 Cm.
EXAMPLE 3 Preparation of 17B-ocet0xy-7a-mpr0pylthi0-4-androsten- I 3-0ne A solution of 1.3 g. of 17fl-acetoxy-4,6-androstadien-3- one, 2 ml. of concentrated hydrochloric acid and 10 ml.
of n-propylmercaptan in ml. of glacial acetic acid is treated according to the procedure described for the preparation or" 17/3-acetoxy-7a-methylthio-4-androsten-3-one 3 (Example 1) to give 17 3-acetoxy-7a-n-propylthio-4-androsten-3-one as white crystals;
AMeOH y (615,100); 111730, 1675, 1622, 1240 cmr' EXAMPLE 4 Preparation of 17p-acetoxy-7a-allylthio-4-andr0sten-3-one A solution of 1 g. of 17/8-acetoxy-4,6-androstadien-3- one, 2 ml. of concentrated hydrochloric acid and 10 ml. of allylmercaptan in 75 ml. of glacial acetic acid is treated according to the procedure described in Example 1 to give 1718-acetoXy-7oiallylthio-4-a.ndrosten-3-one;
rage 241 111; (615,500); 111730, 1675, 1619, 1241 cm.
EXAMPLE 5 Preparation of 17p-acetogcy-7a-n-propylthi0-4-androsten- -one A solution of 0.6 g. of 17/3-acetoxy-4,6-androstadien-3- one, 1 ml. of concentrated hydrochloric acid and 5 ml. of isopropylmercaptan in 25 ml. of glacial acetic acid is treated according to the procedure described in Example 1 to give 17 3-acetoxy-7u-isopropylthio-4-androsten-3-one.
EXAMPLE 6 Preparation of 7a-methylthiotestosterone A solution containing 0.585 g. of 17p-hydroxy-4,6- androstadien-3-one, 1 ml. of concentrated hydrochloric acid and 5 ml. of methylmercaptan in 25 ml. of dioxane is treated according to the procedure described in Example 1, to give 7a-methylthiotestosterone;
max
(e=15,200); 113450, 1670, 1620 cm.-
EXAMPLE 7 Preparation of 7a-methylthiotestosterone propionate A solution of 1.0 g. of 7a-methylthiotestosterone in ml. of reagent pyridine is treated with 5 ml. of propionic anhydride and allowed to stand overnight at room temperature. The mixture is poured into water, extracted with methylene chloride, the methylene chloride extract washed successively with saturated sodium bicarbonate solution and water, and finally evaporated to dryness under reduced pressure to furnish 7a-methylthiotestosterone propionate as white crystals;
max
EXAMPLE 8 Preparation of 7a-methylthiotestosterone isobutyrate A solution of 0.5 g. of 7a-methylthio-testosterone in 5 ml. of reagent pyridine is treated with 3 g. of isobutyric anhydride according to the procedure described in Example 7 to give 7a-methylthiotestosterone isobutyrate;
A 239 mp max (e14,800); 1 1730, 1670, 1625, 1195 cm.-
4 EXAMPLE 9 Preparation of 7a-methy lthiotestosterone benzoate A solution of 0.6 g. of 7a-methylthiotestosterone in 15 m1. of dry benzene is treated with 2 ml. of dry pyridine and 2 g. of benzoyl chlorideand allowed to stand overnight at room temperature. The mixtureis poured into water, extracted with methylene chloride, the methylene chloride extracts washed successively with dilute hydrochloric acid, saturated sodium bicarbonate solution and water, and finally evaporated to dryness under reduced pressure to give 7a-methylthiotestosterone benzoate;
A 228 mp max 1100 cmr EXAMPLE 10 Preparation of 7u-methylthiotestosterone fl-cyclopentylpropionate A solution of 1 g. of 7u-methylthiotestosterone in 25 ml. of dry benzene is treated with 3 ml. of dry pyridine and 3 g. of fl-cyclopentylpropionyl chloride according to the procedure described in Example 9, to give 7a-methylthiotestosterone p-cyclopentylpropionate;
max
(e15,100); 1 1735, 1668, 1620, 1190 cm.-
EXAMPLE 11 Preparation of 7a-methylthiotestosterone decanoate A solution containing 1 g. of 7u-methylthiotestosterone in 25 ml. of dry benzene is treated with 3 ml. of dry pyridine and 4 g. of decanoyl chloride according to the procedure described in Example 10 to give 7oc-methylthiotestosterone decanoate;
by}? 241 my.
We claim: 1. Compounds having the general formula:
O-R CH in which R is a member of the group consisting of hydrogen, lower alkanoyl, cycloalkyl lower alkanoyl and aroyl radicals and R is a member of the group consisting of lower alkyl and lower alkenyl radicals.
2. The compound 175 -acetoxy-7a-methylthio-4androstene-3-one.
3. The compound l7 3-acetoxy 7a allylthio-4-androstene-3-one.
4. The compound 17,8-hydroxy-7a-methylthio-4-androstene-B-one.
5. Compounds having the general formula:
' in which R is a lower alkanoyl radical and R is a lower alkyl radical.
5 6 6. Compounds having the general formula References Cited in the file of this patent OH, UNITED STATES PATENTS OH 011 2,837,543 Dodson et a1. June 3, 1958 5 2,859,222 Dodson et a1. Nov. 4, 1958 0= -S-RI 10 in which R is a lower alkyl radical.
UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,908,694 October 13, 1959 Robert E. Schaub et a1.
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected belm Column 3, line 19, Example 5, for the heading Preparation of JVB-aceZOwy-7apropyZt/Lz'o-4-androsten-3-one read -Preparatz'0n of J7,8-acezfoz'y-7a-is0pr0pyZt/Li0-4- androsten-3one-.
Signed and sealed this 29th day of March 1960.
[sEALJ Attest: KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Oficer. Commissioner of Patents.
Claims (1)
1. COMPOUNDS HAVING THE GENERAL FORMULA:
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US804106A US2908694A (en) | 1959-04-06 | 1959-04-06 | 7-substituted thio-4-androstenes |
| BE589396A BE589396A (en) | 1959-04-06 | 1960-04-05 | New steroids of the androstene series and their preparation |
| GB11973/60A GB917944A (en) | 1959-04-06 | 1960-04-05 | í~-androstenes and method of preparing the same |
| NL250219A NL106961C (en) | 1959-04-06 | 1960-04-06 | |
| DEA34381A DE1128424B (en) | 1959-04-06 | 1960-04-06 | Process for the preparation of 7-alkylthio- and 7-alkenylthio-4-androsten-3-ones |
| FR837366A FR586M (en) | 1959-04-06 | 1960-08-31 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US804106A US2908694A (en) | 1959-04-06 | 1959-04-06 | 7-substituted thio-4-androstenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2908694A true US2908694A (en) | 1959-10-13 |
Family
ID=25188198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US804106A Expired - Lifetime US2908694A (en) | 1959-04-06 | 1959-04-06 | 7-substituted thio-4-androstenes |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US2908694A (en) |
| BE (1) | BE589396A (en) |
| DE (1) | DE1128424B (en) |
| FR (1) | FR586M (en) |
| GB (1) | GB917944A (en) |
| NL (1) | NL106961C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3022323A (en) * | 1962-02-20 | Y-substituted thio steroids of the | ||
| US3074932A (en) * | 1960-08-15 | 1963-01-22 | American Cyanamid Co | 7-substituted thio steroids |
| US3098084A (en) * | 1961-02-02 | 1963-07-16 | Merck Ag E | Anabolic alkylthio-steroids |
| DE1225638B (en) * | 1961-02-02 | 1966-09-29 | Merck Ag E | Process for the preparation of 7alpha-alkylthio-17alpha-methyl-testosterones |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2837543A (en) * | 1956-10-22 | 1958-06-03 | Searle & Co | Pregnene-1-thiol esters and preparation thereof |
| US2859222A (en) * | 1957-12-31 | 1958-11-04 | Searle & Co | 7alpha-acylthio substitution products of 4-androsten-3-ones |
-
1959
- 1959-04-06 US US804106A patent/US2908694A/en not_active Expired - Lifetime
-
1960
- 1960-04-05 BE BE589396A patent/BE589396A/en unknown
- 1960-04-05 GB GB11973/60A patent/GB917944A/en not_active Expired
- 1960-04-06 DE DEA34381A patent/DE1128424B/en active Pending
- 1960-04-06 NL NL250219A patent/NL106961C/xx active
- 1960-08-31 FR FR837366A patent/FR586M/fr active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2837543A (en) * | 1956-10-22 | 1958-06-03 | Searle & Co | Pregnene-1-thiol esters and preparation thereof |
| US2859222A (en) * | 1957-12-31 | 1958-11-04 | Searle & Co | 7alpha-acylthio substitution products of 4-androsten-3-ones |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3022323A (en) * | 1962-02-20 | Y-substituted thio steroids of the | ||
| US3074932A (en) * | 1960-08-15 | 1963-01-22 | American Cyanamid Co | 7-substituted thio steroids |
| US3098084A (en) * | 1961-02-02 | 1963-07-16 | Merck Ag E | Anabolic alkylthio-steroids |
| DE1225638B (en) * | 1961-02-02 | 1966-09-29 | Merck Ag E | Process for the preparation of 7alpha-alkylthio-17alpha-methyl-testosterones |
Also Published As
| Publication number | Publication date |
|---|---|
| FR586M (en) | 1961-06-12 |
| GB917944A (en) | 1963-02-13 |
| NL106961C (en) | 1963-11-16 |
| BE589396A (en) | 1960-10-05 |
| DE1128424B (en) | 1962-04-26 |
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